The present invention relates to supported catalyst systems obtainable by
A) reaction of an inorganic carrier with a metal compound of the general formula I
M1(R1)r(R2)s(R3)t(R4)uxe2x80x83xe2x80x83I
xe2x80x83where
M1 is an alkali metal, an alkaline earth metal or a metal of main group III or IV of the Periodic Table,
R1 is hydrogen, C1-C10-alkyl, C6-C15-aryl, alkylaryl or arylalkyl, each having 1 to 10 carbon atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical,
R2 to R4 are each hydrogen, halogen, C1-C10-alkyl, C6-C15-aryl, alkylaryl, arylalkyl, alkoxy or dialkylamino, each having 1 to 10 carbon atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical,
r is an integer from 1 to 4 and
s, t and u are integers from 0 to 3, the sum r+s+t+u corresponding to the valency of M1,
B) reaction of the material obtained according to A) with a metallocene complex in its metal dihalide form and a compound forming metallocenium ions and
C) subsequent reaction with a metal compound of the general formula II
M2(R5)0(R1)p(R1)qxe2x80x83xe2x80x83II
xe2x80x83where
M2 is an alkali metal, an alkaline earth metal or a metal of main group III of the Periodic Table,
R5 is hydrogen, C1-C10-alkyl, C6-C15-aryl, alkylaryl or arylalkyl each having 1 to 10 carbon atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical,
R6 and R7 are each hydrogen, halogen, C1-C10-alkyl, C6-C15-aryl, alkylaryl, arylalkyl or alkoxy, each having 1 to 10 carbon atoms in the alkyl radical and 6 to 20carbon atoms in the aryl radical,
o is an integer from 1 to 3 and
p and q are integers from 0 to 2, the sum o+p+q corresponding to the valency of M2.
The present invention furthermore relates to processes for the preparation of such supported catalyst systems and their use for the preparation of polyolefins.
In recent years, homogeneous metallocene catalysts have made it possible to obtain well defined poly-l-olefins having a narrow molecular weight distribution and high chemical uniformity. However, industrial use necessitates the conversion of these catalysts to heterogeneous form so that simple handling of the catalyst and effective control of the morphology of the product are ensured. Supported metallocene catalysts are known per se. Thus, EP-A 323 716 describes those systems in which moist SiO2 is reacted with a trialkyl aluminum to give an alumoxane-laden carrier. The metallocene is applied to this carrier, an active catalyst being formed.
WO 91/09882 discloses the preparation of a supported, cationic metallocene catalyst by applying the reaction mixture of the dialkylmetallocene with an ionic compound, which has a Bronsted acid as the cation and a noncoordinating opposite ion, such as tetrakis(pentafluorophenyl)borate, as the anion, to an inorganic carrier. Here too, an active catalyst is obtained.
Similar supported catalyst systems are also disclosed in WO 94/03506 and WO 95/14044.
EP-A 628 574 describes supported catalyst systems in which a metallocene dihalide is reacted with an alkyl aluminum in the presence of a hydridoborate and this solution, which is active with respect to polymerization, is applied to a carrier.
Such catalysts which are already active readily give rise to problems in the metering of the catalyst into the reactor.
What is therefore advantageous is a catalyst which is still inactive and cannot be activated until a later stage, for example during metering or in the reactor itself.
EP-A 613 908 discloses supported metallocene catalyst systems, some of which are not activated until they are in the reactor. Here, however, the polymers formed have a broad molecular weight distribution Mw/Mn.
WO 95/15815 describes catalysts which are obtained by supporting a metallocene dichloride and a borate on a crosslinked polymer. The use of deactivated inorganic carriers gives catalysts which, after activation in the polymerization reactor, have either only slight activity or no activity at all.
It is an object of the present invention to provide supported catalyst systems which do not have the stated disadvantages, in particular can be activated at any desired time, are air- and moisture-insensitive, can be stored for a long time and are not flammable, the polymers formed having a narrow molecular weight distribution.
We have found that this object is achieved by the supported catalyst systems defined at the outset.
We have furthermore found processes for the preparation of such supported catalyst systems and their use for the preparation of polyolefins.
The novel supported catalyst systems are obtainable by reacting an inorganic carrier with a metal compound of the general formula I in a first stage A).
Preferably used carriers are finely divided solids whose particle diameters are from 1 to 200 xcexcm, in particular from 30 to 70 xcexcm.
Examples of suitable carriers are silica gels, preferably those of the formula SiO2 a Al2O3, where a is from 0 to 2, preferably from 0 to 0.5; these are therefore aluminosilicates or silica.
Such products are commercially available, for example Silica Gel 332 from Grace.
Other inorganic compounds, such as Al2O3 or MgCl2, or mixtures containing these compounds may also be used as carriers.
Preferred metal compounds of the general formula I are those in which M1 is a metal of main group III of the Periodic Table, in particular aluminum, R1 is C1-C10-alkyl and R2 to R4 are each C1-C10-alkyl. For the particularly preferred case where M1 is aluminum, u is zero and R1 to R3 have in particular the same meaning, preferably methyl, ethyl, isobutyl or hexyl, preferably isobutyl.
Preferably, the metal compound of the general formula I is added as a solution to a suspension of the carrier. Particularly suitable solvents or suspending agents are hydrocarbons, such as heptane. The amount of metal compound I may be varied within wide limits, the minimum amount depending on the number of hydroxyl groups of the carrier. The temperatures, reaction times and pressures are not critical per se, temperatures of from 0 to 80xc2x0 C. and reaction times of from 0.1 to 48 hours being preferred.
It has proven suitable to remove the excess metal compound I by thorough washing, for example with hydrocarbons, such as pentane or hexane, after the carrier pretreatment and to dry the carrier.
The material thus prepared can be stored for up to 6 months and is not pyrophoric.
This material is then reacted, in a further stage B), with a metallocene complex in its metal dihalide form and a compound forming metallocenium ions.
Examples of suitable metallocene complexes are the following compounds of the general formula III: 
where
M is titanium, zirconium, hafnium, vanadium, niobium or tantalum,
x is fluorine, chlorine, bromine or iodine,
R8 to R12 are each hydrogen, C1-C10-alkyl, 5- to 7-membered cycloalkyl which in turn may carry a C1-C10-alkyl as a substituent, C6-C15-aryl or arylalkyl, where two adjacent radicals together may furthermore form a cyclic group of 4 to 15 carbon atoms, or Si(R13)3, where
R13 is C1-C10-alkyl, C3-C10-cycloalkyl or C6-C15-aryl, and
z is X or 
where
R14 to R18 are each hydrogen, C1-C10-alkyl, 5- to 7-membered cycloalkyl which in turn may carry a C1-C10-alkyl as a substituent, C6-C15-aryl or arylalkyl, where two adjacent radicals together may furthermore form a cyclic group of 4 to 15 carbon atoms, or Si(R19)3, where
R19 is C1-C10-alkyl, C6-C15-aryl or C3-C10-cycloalkyl,
or where R11 and Z together form a group xe2x80x94R20xe2x80x94Axe2x80x94, where 
xe2x80x83xe2x95x90BR22, xe2x95x90AlR22, xe2x80x94Gexe2x80x94, xe2x80x94Snxe2x80x94, xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, xe2x95x90SO, xe2x95x90SO2, xe2x95x90NR22, xe2x95x90CO, xe2x95x90PR22 or xe2x95x90P(O)R22,
where R21, R22 and R23 are identical or different and are each hydrogen, halogen, C1-C10-alkyl, C1-C10-fluoroalkyl, C6-C10-fluoroaryl, C6-C10-aryl, C1-C10-alkoxy, C2-C10-alkenyl, C7-C40-arylalkyl, C8-C40-arylalkenyl or C7-C40-alkylaryl or where two adjacent radicals together with the atoms linking them may form a ring, and
M3 is silicon, germanium or tin, 
R24 is C1-C10-alkyl, C6-C15-aryl, C3-C10-cycloalkyl, alkylaryl or Si(R25)3 and
R25 is hydrogen, C1-C10-alkyl, C6-C15-aryl, which in turn may be substituted by C1-C4-alkyl, or C3-C10-cycloalkyl
or where R11 and R17 together form a group xe2x80x94R20xe2x80x94.
Among the metallocene complexes of the general formula III, 
are preferred.
The radicals X may be identical or different but are preferably identical.
Particularly preferred compounds of the formula IIIa are those in which
M is titanium, zirconium or hafnium,
X is chlorine and
R8 to R12 are each hydrogen or C1-C4-alkyl.
Preferred compounds of the formula IIIb are those in which
M is titanium, zirconium or hafnium,
X is chlorine,
R8 to R12 are each hydrogen, C1-C4-alkyl or Si(R13)3 and
R14 to R18 are each hydrogen, C1-C4-alkyl or Si(R19)3.
Particularly suitable compounds of the formula IIIb are those in which the cyclopentadienyl radicals are identical.
Examples of particularly suitable compounds include bis(cyclopentadienyl)zirconium dichloride, bis(pentamethylcyclopentadienyl)zirconium dichloride, bis(methylcyclopentadienyl)zirconium dichloride, bis(ethylcyclopentadienyl)zirconium dichloride, bis(n-butylcyclopentadienyl)zirconium dichloride and bis(trimethylsilylcyclopentadienyl)zirconium dichloride.
Particularly suitable compounds of the formula IIIc are those in which
R8 and R14 are identical and are each hydrogen or C1-C10-alkyl,
R12 and R18 are identical and are each hydrogen, methyl, ethyl, isopropyl or tert-butyl, R10 and R16 are C1-C4-alkyl R9 and R15 are each hydrogen or two adjacent radicals R9 and R10 on the one hand and R15 and R16 on the other hand together form a cyclic group of 4 to 12 carbon atoms, 
M is titanium, zirconium or hafnium and
x is chlorine.
Examples of particularly suitable complex compounds include dimethylsilanediylbis(cyclopentadienyl)zirconium dichloride, dimethylsilanediylbis(indenyl)zirconium dichloride, dimethylsilanediylbis(tetrahydroindenyl)zirconium dichloride, ethylenebis(cyclopentadienyl)zirconium dichloride, ethylenebis(indenyl)zirconium dichloride, ethylenebis(tetrahydroindenyl)zirconium dichloride, tetramethylethylene-9-fluorenylcyclopentadienylzirconium dichloride, dimethylsilanediylbis(-3-tert-butyl-5-methylcyclopentadienyl)zirconium [sic] dichloride, dimethylsilanediylbis(-3-tert-butyl-5-ethylcyclopentadienyl)zirconium [sic] dichloride, dimethylsilanediylbis(-2-methylindenyl)zirconium [sic] dichloride, dimethylsilanediylbis(-2-isopropylindenyl)zirconium [sic] dichloride, dimethylsilanediylbis(-2-tert-butylindenyl)zirconium [sic] dichloride, diethylsilanediylbis(-2-methylindenyl)zirconium [sic] dibromide, dimethylsilanediylbis(-3-methyl-5-methylcyclopentadienyl)zirconium [sic] dichloride, dimethylsilanediylbis(-3-ethyl-5-isopropylcyclopentadienyl)zirconium [sic] dichloride, dimethylsilanediylbis(-2-methylindenyl)zirconium [sic] dichloride, dimethylsilanediylbis(-2-methylbenzindenyl)zirconium [sic] dichloride and dimethylsilanediylbis(-2-methylindenyl)hafnium [sic] dichloride.
Particularly suitable compounds of the general formula IIId are those in which
M is titanium or zirconium,
X is chlorine, 
and
R8 to R10 and R12 are each hydrogen, C1-C10-alkyl, C3-C10-cycloalkyl, C6-C15-aryl or Si(R14)3, or where two adjacent radicals form a cyclic group of 4 to 12 carbon atoms.
The synthesis of such complex compounds can be carried out by methods known per se, the reaction of the appropriately substituted, cyclic hydrocarbon anions with halides of titanium, zirconium, hafnium, vanadium, niobium or tantalum being preferred.
Examples of appropriate preparation processes are described, inter alia, in J. Organometal. Chem., 369 (1989), 359-370.
Mixtures of different metallocene complexes may also be used.
Particularly suitable compounds forming metallocenium ions are strong, neutral Lewis acids, ionic compounds having Lewis acid cations and ionic compounds having Bronsted acids as cations.
Preferred strong, neutral Lewis acids are compounds of the general formula IV
M4X1X2X3xe2x80x83xe2x80x83IV
where
M4 is an element of main group III of the Periodic Table, in particular B, Al or Ga, preferably B, and
X1, X2 and X3 are each hydrogen, C1-C10-alkyl, C6-C15-aryl, alkylaryl, arylalkyl, haloalkyl or haloaryl, each having 1 to 10 carbon atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical, or fluorine, chlorine, bromine or iodine, in particular haloaryl, preferably pentafluorophenyl.
Particularly preferred compounds of the general formula IV are those in which X1, X2 and X3 are identical, preferably tris(pentafluorophenyl)borane.
Suitable ionic compounds having Lewis acid cations are compounds of the general formula V
[(Ya+)Q1Q2 . . . Qz]d+xe2x80x83xe2x80x83V
in which
Y is an element of main group I to VI or subgroup I to VIII of the Periodic Table,
Q1 to Qz are radicals having a single negative charge, such as C1-C28-alkyl, C6-C15-aryl, alkylaryl, arylalkyl, haloalkyl, haloaryl each having 6 to 20 carbon atoms in the aryl radical and 1 to 28 carbon atoms in the alkyl radical, C1-C10-cycloalkyl, which may be substituted by C1-C10-alkyl, or halogen, C1-C28-alkoxy, C6-C15-aryloxy, silyl or mercaptyl,
a is an integer from 1 to 6,
z is an integer from 0 to 5 and
d corresponds to the difference axe2x88x92z, but d is greater than or equal to 1.
Carbonium cations, oxonium cations and sulfonium cations and cationic transition metal complexes are particularly suitable. Particular examples are the triphenylmethyl cation, the silver cation and the 1,1xe2x80x2-dimethylferrocenyl cation. They preferably have noncoordinating opposite ions, in particular borane compounds, as also stated in WO 91/09882, preferably tetrakis(pentafluorophenyl)borate.
Ionic compounds having Bronsted acids as cations and preferably also noncoordinating opposite ions are stated in WO 91/09882, a preferred cation being N,N-dimethylanilinium.
The amount of compounds forming metallocenium ions is preferably from 0.1 to 10 equivalents, based on the metallocene complex III.
The conditions for the reaction with the metallocene complex with the compound forming metallocenium ions are not critical per se; the reaction is preferably carried out in solution, particularly suitable solvents being hydrocarbons, preferably aromatic hydrocarbons, such as toluene.
The material prepared according to A) is then added to this. An amount of from 0.1 to 10% by weight, based on the inorganic carrier, of metallocene complex is particularly suitable. The conditions for this reaction are likewise not critical, temperatures of from 20 to 80xc2x0 C. and reaction times of from 0.1 to 20 hours having proven particularly suitable.
The material obtained according to B) can then be isolated and can be stored for up to at least 6 months.
In a further stage C), the activation stage, the material obtained according to B) is reacted with a metal compound of the general formula II. This activation can be carried out at any desired time, i.e. before, during or after the metering of the material obtained according to B) in the reactor. The activation is preferably carried out after the metering of the material obtained according to B) into the reactor.
Among the metal compounds of the general formula II
M2(R5)o(R6)p(R7)qxe2x80x83xe2x80x83II
where
M2 is an alkali metal, an alkaline earth metal or a metal of main group III of the Periodic Table, ie. boron, aluminum, gallium, indium or thallium,
R5 is hydrogen, C1-C10-alkyl, C6-C15-aryl, alkylaryl or arylalkyl each having 1 to 10 carbon atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical,
R6 and R7 are each hydrogen, halogen, C1-C10-alkyl, C6-C15-aryl, alkylaryl, arylalkyl or alkoxy each having 1 to 10 carbon atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical,
o is an integer from 1 to 3 and
p and q are integers from 0 to 2 the sum o+p+q corresponding to the valency of M2,
preferred compounds are those in which
M2 is lithium, magnesium or aluminum and
R5 to R7 are each C1-C10-alkyl.
Particularly preferred metal compounds of the general formula II are n-butyl lithium, n-butyl-n-octyl magnesium, n-butyl-n-heptyl magnesium and tri-n-hexyl aluminum.
The conditions for the reaction in stage C) are not critical per se. Temperatures, reaction times and pressures depend on the time when the reaction, ie. activation, is carried out.
With the aid of these novel supported catalyst systems, it is possible to prepare polyolefins, in particular polymers of alk-1-enes. These are understood as meaning homo- and copolymers of C2-C10-alk-1-enes, preferably used monomers being ethylene, propylene, but-1-ene, pent-1-ene and hex-1-ene.
However, cycloolefins or higher alk-1-enes and alkenes generally may also be used as monomers for the homo- or copolymerization.
The novel supported catalyst systems are distinguished in particular by high activity, can be activated at any desired time, can be stored for a long time, are not pyrophoric and can therefore be easily handled and lead to polymers having a narrow molecular weight distribution.